Method for fighting against arthropods destructive of crops and compositions therefor

ABSTRACT

The present invention relates to processes for controlling arthropods, particularly processes for controlling insects and especially processes for controlling insects which ravage crops, particularly rice crops or market-garden crops; as well as to processes for protecting crops, particularly rice crops or market-garden crops; as well as to processes directed towards improving the yield of the treated crops; as well as to compositions or products which may be used in such processes.

DESCRIPTION

The present invention relates to processes for controlling arthropods,particularly processes for controlling insects and especially processesfor controlling insects which ravage crops, particularly rice crops ormarket-garden crops; as well as to processes for protecting crops,particularly rice crops; as well as to processes directed towardsimproving the yield of the treated crops; as well as to compositions orproducts which may be used in such processes.

More specifically, the present invention relates to processes asmentioned above which use specific insecticidal compounds in combinationwith other insecticidal compounds that are also specific; these areusually processes combining, in a particularly advantageous manner, theaction of an insecticidal compound (A) comprising a pyrazole group andthe action of an insecticidal compound (B), particularly an insecticidalcompound of the pyrethroid family.

The literature discloses processes using a wide variety of insecticidalcompounds. However, the known insecticidal compounds used in suchprocesses, although having certain insecticidal effects, often do notmake it possible to overcome numerous problems encountered by the usersof such products, in particular users seeking specific solutionstailored to quite specific uses.

International patent application WO 95/22902 is known, which disclosescertain insecticidal processes that are useful for controlling termitesand which use certain specific compounds of the fiprole family withpyrethroids.

Processes for controlling certain specific types of chrysomeles whichattack corn crops, and which use a specific pyrazole with certaincompounds of the pyrethroid family, are also known from American patentapplication Ser. No. 09/396,331.

However, these patent applications do not make it possible to providesatisfactory solutions to the problems which may be encountered incombating or controlling insects which ravage crops, in particular bymeans of specific insecticidal processes.

One of the problems encountered in the protection of crops againstharmful arthropods, and in particular insect pests, lies in the need toreduce the amounts of active ingredient used whilst allowing asatisfactory, if not greater, efficacy to be obtained. Indeed, it iscommon to broadcast or employ large amounts of the said insecticidalactive ingredients.

Another problem encountered concerns the need to have available activeingredients which are effective against a broad spectrum of insect pestscapable of damaging or damaging crops.

Another problem relates to the effect over time of the activeingredients employed for the protection of crops: it is desirable bothto have active ingredients possessing an immediate, or virtuallyimmediate, insecticidal activity following application to the crops, andalso that these said active ingredients possess an insecticidal effectwhose duration is sufficient to allow effective and lasting protectionof the crops against insect pests.

Another problem lies in the fact that certain insecticidal activeingredients do not possess an immediate insecticidal effect but act onlyafter a certain period of time has elapsed following application,thereby allowing the populations of insect pests to multiply before theactive ingredient utilized takes effect.

Another problem encountered with a considerable number of insecticidalactive ingredients is that they have only a curative effect, thereforeobliging the user to undertake demanding and careful monitoring of thecrops in order to determine the exact time of treatment.

Another problem of significance is that a number of insecticidal activeingredients have only a preventive effect, therefore forcing the user tobroadcast amounts of these active ingredients which, subsequently, proveto be useless.

Another problem associated with the use of certain insecticidal activeingredients resides in the phenomenon of resurgence of the populationsof insect pests treated, a phenomenon which is critical to the user, whoinitially sees the populations of harmful organisms reduced aftertreatment but then, subsequently, sees these populations grow again.Although this phenomenon of resurgence is not frequent, it is extremelydamaging when it does occur.

Another problem which lies in the use of certain known insecticidalcompounds is the difficulty of finding a means for effectivelycontrolling a group of several insect pests liable to attack a specificcrop.

In particular, it is especially difficult to provide a means ofeffective insecticidal control for a set of insect pests which ravagerice crops, especially a means of controlling insect pests of thefamilies Delphacidae, Noctuidae, Plutellidae, Pyralidae, Tortricidae.

The numerous problems which have been set out above are very oftenaccompanied by those associated with the protection of the environment,environmental problems to which the users of insecticidal activeingredients are more and more sensitive, as are the consumers of theproducts obtained from these crops.

Another difficulty in relation to the use of many insecticides lies inthe cumulative effect of two or more of the problems which have been setout above. Indeed, it is even more difficult to solve the problems whichhave arisen when they accumulate, since the solutions which may beconsidered are in some cases contradictory or even conflictive.

Moreover, and of a general nature, it is always desirable to improve thespectrum of activity and the efficacy of compounds having aninsecticidal action, or to reinforce the said spectra of activity and ofefficacy, by combining the said compounds in order to obtain ahigher-performance product or combination, as well as processes forcombating or controlling insects which ravage crops, these processesbeing optimally tailored to the specific requirements of the users.

It is also desirable to prevent the appearance of resistances to theseinsecticides on the part of insect pests.

It is likewise always desirable to provide the user of theseinsecticidal compounds with an increased range of insecticidal means forcombating or controlling insect pests, particularly in the field ofagriculture, owing in particular to the devastation which these insectpests can wreak on crops.

It is likewise highly desirable to improve or better control the rate orpersistency of action of these insecticidal compounds.

It is likewise always desirable to provide the user of theseinsecticidal compounds with means of combating or controlling insectpests under specific conditions of use, especially in accordance withthe environment of the crops to be protected or in accordance with thecrops or the insect pests damaging or damaging these crops, oralternatively according to the degree of infestation with these insectpests.

It is also most desirable to provide insecticidal control means whichpossess a so-called knockdown insecticidal effect, the said knockdowneffect consisting, in the sense of the present text, in a rapid effectof the insecticidal action, usually measured by a rapid decrease in thenumber of insects. Such a knockdown effect is preferably recognized foractive materials whose satisfactory insecticidal action appears within afew hours.

It is likewise desirable to allow a persistency of action over time ofthe insecticidal action of the insecticidal active ingredients employed.

The present invention therefore proposes to provide solutions to all orpart of the many problems which have been set out above. The presentinvention also proposes to attain all or part of the objectives whichhave been referred to.

An essential aspect of the present invention relates to specificprocesses for treating and controlling crop-damaging arthropods,preferentially insecticidal processes, which use an insecticidalcompound (A) containing a pyrazole group, and an insecticidal compound(B) of the pyrethroid family.

Preferentially, the processes according to the present invention areadvantageously carried out in the agricultural sector, particularly forplant protection.

Advantageously, the protection or treatment processes according to thepresent invention use an insecticidal compound (A) of the phenylpyrazolefamily.

More advantageously, the said processes according to the invention usean insecticidal compound (A) of formula (I)

in which:

R₁ represents —CN or the methyl radical or the radical —C(S)NH₂ or theradical —C(═N—Y)Z;

R₂ represents —S(O)_(n)R₃;

R₃ represents an alkyl or haloalkyl radical;

R₄ is selected from the group consisting of a hydrogen atom, a halogenatom and a radical which can be —NR₅R₆, —C(O)OR₇, —S(O)_(m)R₇, alkyl,haloalkyl, —OR₈ or —N═C(R₉)(R₁₀);

R₅ and R₆ are selected independently from a hydrogen atom, an alkyl orhaloalkyl radical, —C(O)alkyl, —C(O)OR₇ and —S(O)_(r)CF₃; or R₅ and R₆together form a divalent radical which can be interrupted by one or moreheteroatoms;

R₇ is selected from an alkyl radical and a haloalkyl radical;

R₈ is selected from an alkyl radical, a haloalkyl radical and a hydrogenatom;

R₉ is selected from a hydrogen atom and an alkyl radical;

R₁₀ is selected from a phenyl and heteroaryl radical optionallysubstituted with one or more hydroxyl radicals, halogen atoms,—O-alkyls, —S-alkyls, cyano or alkyl radicals or a combination thereof;

X is selected from the nitrogen atom and the radical C—R₁₂;

Y is selected from the hydroxyl, amino, aminocarbonyl, alkoxy,arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl,alkylcarbamoyl and pyrazole groups, substituted or unsubstituted;

Z is selected from the hydroxyl, amino, aminocarbonyl, alkoxy,arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyland alkylcarbamoyl groups;

R₁₁ and R₁₂ are selected independently from a halogen atom and ahydrogen atom;

R₁₃ is selected from a halogen atom, a haloalkyl or haloalkoxy radical,—S(O)_(q)CF₃ and —SF₅;

m, n, q and r are selected independently from 0, 1 and 2;

with the proviso that, if R₁ represents the methyl radical, then R₃represents a haloalkyl radical, R₄ represents —NH₂, R₁₁ represents Cl,R₁₃ represents —CF₃ and X represents N;

the alkyl and alkoxy radicals of the formula (I) are preferably loweralkyl and alkoxy radicals, i.e. radicals possessing from one to fourcarbon atoms;

the haloalkyl and haloalkoxy radicals likewise possess preferably fromone to four carbon atoms;

the haloalkyl and haloalkoxy radicals can carry one or more halogenatoms; the preferred radicals of this type comprise —CF₃ and —OCF₃.

According to one preferred variant, the processes according to theinvention use an insecticidal compound (A) of formula (I) in which:

R₁ represents —CN; and/or

R₄ represents —NR₅R₆; and/or

R₅ and R₆ are selected independently from a hydrogen atom, an alkyl orhaloalkyl radical and —C(O)alkyl; and/or

X represents —C—R₁₂; and/or

R₁₃ is selected from a halogen atom, a haloalkyl or haloalkoxy radicaland —SF₅.

According to one especially advantageous variant, the protection ortreatment processes according to the invention use Fipronil, chemicalname5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole,as insecticidal compound (A).

According to another advantageous embodiment of the processes accordingto the invention, the compound (B) used is a compound of formula (II)

in which:

R₁ and R₂ represent, independently, a C₁ to C₈ alkyl radical or a C₁ toC₈ haloalkyl radical or a halogen atom or a substituted or unsubstitutedphenyl group; and/or

R₃ represents a —CN group or a hydrogen atom or a C₁ to C₈ alkylradical; and/or

R₄ represents a substituted or unsubstituted phenyl group.

According to another advantageous embodiment, the compound (B) used inthe processes according to the invention is a compound of formula (II)in which:

R₁ and R₂ represent, independently, a bromine atom or a chlorine atom ora methyl radical or an isopropyl radical or a para-chlorophenyl radicalor a trifluoromethyl radical; and/or

R₄ represents a substituted or unsubstituted phenoxybenzyl group.

According to another advantageous embodiment, the compound (B) used forthe processes according to the invention is a compound of formula (II)in which:

R₄ represents a halophenoxybenzyl group.

Where appropriate, and during its use in processes according to theinvention, the compound (B) of formula (II) may be either in the form ofa specific isomer or in the form of a mixture of several isomers, oreven in the form of a mixture of several compounds of formula (II).

However, as regards the compounds of the pyrethroid family which areused as insecticidal compound (B) during the use of the protection ortreatment processes according to the invention, the compounds preferablyused are those chosen from the group comprising

bifenthrin or2-methylbiphenyl-3-ylmethyl-(Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate;

cyfluthrin or (R,S)-α-cyano-4-fluoro-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

cyhalothrin or (R,S)-α-cyano-3-phenoxybenzyl(Z)-(1RS,3RS)-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate;

cypermethrin or (R,S)-α-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

alpha-cypermethrin or racemic mixture comprising(S)-α-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(R)-α-cyano-3-phenoxybenzyl(1S,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

beta-cypermethrin or reaction mixture comprising, in a 2:3 ratio, the 2enantiomeric pairs (S)-α-cyano-3-phenoxybenzyl(1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(R)-α-cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate with(S)-α-cyano-3-phenoxybenzyl(1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(R)-α-cyano-3-phenoxybenzyl(1S)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

theta-cypermethrin or mixture of the enantiomers(R)-α-cyano-3-phenoxybenzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(S)-α-cyano-3-phenoxybenzyl(1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate in a1:1 ratio;

zeta-cypermethrin or mixture of the stereoisomers(S)-α-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,in which mixture the ratio of the enantiomeric pairs (S)-(1RS,3RS) and(S)-(1RS,3SR) is, respectively, between 45/55 and 55/45;

deltamethrin or (S)-α-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate;

fenpropathrin or (RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate;

fenvalerate or (RS)-α-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methylbutyrate;

flumethrin or α-cyano-4-fluoro-3-phenoxybenzyl;

permethrin or 3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

phenothrin or 3-phenoxybenzyl(1RS,3RS;1RS,3SR)-2,2-dimethyl-3-(2-methylprop-1-enyl)-cyclopropanecarboxylate;

tefluthrin or 2,3,5,6-tetrafluoro-4-methylbenzyl(Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate;

tralomethrin or (S)-α-cyano-3-phenoxybenzyl(1R,3S)-2,2-dimethyl-3-[(RS)-1,2,2,2-tetrabromoethyl]cyclopropanecarboxylate;

flucythrinate or (RS)-α-cyano-3-phenoxybenzyl(S)-2-(4-difluoromethoxyphenyl)-3-methylbutyrate;

tau-fluvalinate or (RS)-α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate.

Moreover, the compounds of the pyrethroid family which may be used whencarrying out the processes according to the invention are, for some ofthem, known per se as having certain insecticidal properties or ashaving insecticidal activity, while at the same time being acceptablefor agricultural uses, in particular for treating or protecting crops.

In the different process variants according to the present invention,the insecticidal compounds (A) and (B) are used in effective butnon-phytotoxic doses.

As regards the insecticidal compounds (A) containing a pyrazole group,which are used in the various processes according to the presentinvention, reference may also be made to those disclosed, respectively,in the European patents or patent applications EP-A-0 295 117, EP-A-0460 940 or EP-A-0 484 165; as well as in International patentapplication WO 98/28279.

Reference may moreover be made to the book The Electronic PesticideManual version 1.0 (from the British Crop Protection Council, edited byClive Tomlin) as regards processes for preparing the insecticidalcompounds (B).

Except where otherwise mentioned and throughout the present text, theinsecticidal compounds (A) and (B) used may be denoted, withoutpreference, by any one of the following expressions: active materials orcompounds or insecticidal compounds or active substances or insecticidalsubstances, without, however, departing from the spirit of the presentinvention, especially on account of the insecticidal properties of thesecompounds, substances or materials.

Preferably, and for their use in practise when carrying out theprocesses according to the present invention, the various insecticidalsubstances (A) and (B) described above are rarely used alone.

Thus, for their use in the processes according to the invention, theinsecticidal active materials (A) and (B) are usually combined with asolid or liquid support, which can be used especially in theagricultural sector, and optionally with at least one surfactant and/orone or more auxiliary agents.

These processes according to the invention, which are useful inparticular for protecting plants against insects, use as active materialat least one of the insecticidal compounds (A) or (B) as describedabove, advantageously in combination with agriculturally acceptablesolid or liquid supports and/or surfactants that are also agriculturallyacceptable.

In particular, supports which may be used are the common inert supports;similarly, surfactants which may be used are the surfactants that arecommon in the formulation of compositions intended for agricultural use,in particular for treating or protecting crops, such as those of thepresent invention.

A more detailed description of the various compounds or adjuvants which,for the purposes of the present invention, may be combined with thecompounds (A) and (B) will be the subject of a specific developmentlater in the present text.

Usually, the processes according to the invention use formulationscomprising between 0.00001% and 100%, preferably between 0.001% and 80%,of insecticidal compounds (A) and (B), whether these compounds arecombined or are in the form of two active materials used separately.

Usually, however, the processes according to the invention combine aninsecticidal compound (A) and an insecticidal compound (B)simultaneously.

Except where otherwise mentioned, the proportions and percentages usedor described throughout the present description and in the claims whichfollow are proportions or percentages on a weight basis.

More generally, when they are used in the processes according to theinvention, the insecticidal compounds (A) and (B) may be combined withany solid or liquid additive corresponding to the usual formulationtechniques, particularly the formulation of products or compositionsintended for uses or utilizations in agriculture.

Among the treatment and/or protection processes or methods according tothe invention, the ones which are preferred are those which are used fortreating and/or protecting crops.

The said use of the processes according to the invention can be carriedout according to various forms and in particular using quite a widevariety of application methods, but also according to differentapplication techniques, or alternatively to protect different types,varieties or families of vegetation or plants, or alternatively tocombat or control different types or species of arthropods, especiallyinsect pests.

As regards the various application methods carried out beneficially inthe processes according to the invention, simultaneous, separate,alternating or sequential application methods are especially possible.

Usually, however, the application methods that are beneficial in theprocesses according to the invention and which are preferred consist ofmethods for applying the insecticidal compounds (A) and (B)simultaneously.

However, a relatively advantageous variant of a process according to theinvention uses a method of alternate application of the insecticidalcompounds (A) and (B).

Another application method which is useful for carrying out theprocesses according to the invention relates to the sequentialapplication of the insecticidal compounds (A) and (B); such a sequentialapplication method may especially take the form of several applicationsof insecticidal compound (A), followed by several applications ofinsecticidal compound (B). Needless to say, a reversed sequentialapplication method consisting of several applications of insecticidalcompound (B) followed by several applications of insecticidal compound(A) also forms a part of the processes of the present invention.

The different variants for carrying out the processes according to theinvention which have just been described may also be combined orassociated, in whole or in part, with one another. A person skilled inthe art will readily know how to determine the associations orcombinations of application methods according to the invention whichbest suit the use of the insecticidal compounds (A) and (B) which heenvisages.

Besides the various methods for carrying out the processes according tothe invention which have just been described, the said processes canalso use a relatively large number of application techniques; thus,among the said techniques which may be mentioned in particular aredusting, dipping, spraying, smoking or misting, etc.

Other variants of the application methods that are useful for theprocesses according to the invention exist, particularly depending onthe part(s) of the plant or vegetation which is (are) to be treated.

Thus, the processes according to the invention can be carried out forthe treatment or protection of the plant propagation material or theseeds, in particular the grains, the tubers or the rhizomes; for thetreatment of the roots, or for the treatment of the stems or leaves ofthe plant; as well as for the treatment of the roots, or alternativelyof the fruits or other parts of the plant having a substantial economicor agronomic value.

Furthermore, the said processes according to the invention may becarried out for the treatment of plants at numerous stages in theirdevelopment, in particular for the treatment of seeds, seedlings orplanted-out seedlings, planted-out plants, or plants.

The processes which are carried out for the treatment of the soil undercultivation or to be cultivated also form a part of the presentinvention.

However, and in a particularly advantageous manner, the processesaccording to the invention use the insecticidal compounds (A) and (B)for treatment by foliar application to the plant to be treated. Evenmore advantageously, such a treatment is carried out by spraying.

Likewise, said processes according to the invention for seed treatmentare particularly advantageous.

The processes for treating or protecting plants according to theinvention by means of the insecticidal compounds (A) and (B) areparticularly advantageous when carried out for the treatment orprotection of cereal or market-garden crops, particularly rice, wheat,barley or rye, as well as for the treatment or protection of corn,sorghum, sunflower, soybean, or alternatively cotton, pea, rape, potato,vegetable or fruit crops, beet, onions, cabbages, tomatoes, beans,lettuces, etc.

The said processes for treating or protecting plants according to theinvention give particularly advantageous results when used for thetreatment of rice. Particularly advantageous results are obtained withnumerous varieties of rice, whether or not these varieties are hybridvarieties. The processes according to the invention that arebeneficially carried out for the treatment or protection of the varietyOryza sativa also give highly satisfactory results.

As may emerge from the preceding development of the present text, theprocesses according to the invention may be useful both for preventivetreatments and for curative treatments.

The processes according to the invention using an insecticidal compound(A) and an insecticidal compound (B) are advantageously carried out tocombat or control harmful arthropods, especially harmful insects.

Thus, the said processes according to the invention are advantageouslyemployed for combating or controlling insects of the familiesDelphacidae sp., especially Nilaparvata lugens, Nilaparvata oryzae andSogatella furcifera; and/or Cicadellidae sp. especially Empoascadecipiens, Nephotettix apicalisi, Nephotettix impicticeps, Nephotettixcincticeps and Nilaparvata oryzae; and/or Pyralidae sp., especiallyTryporyza incertulas, Tryporyza innotata, Cnaphalocrosis medinalis,Chilo loftini, Chilo suppressalis, Chilo indicus and Chilotraeaplejadellus; Tylenchidae sp., especially Ditylenchus dipsaci,Ditylenchus angustus and Ditylenchus radicicolus; and/or Noctuidae sp.,especially Sesamia interens, Sesamia calamistis and Sesamia cretica;and/or Pentatomidae sp. especially Scotinophara lurida and Scotinopharacoarctata; and/or Plutellidae sp. especially Plutella xylostella; and/orTortricidae sp. especially Archips breviplicanus; and/or Cecidomyiidaesp. especially Orselia oryzae and Pachydiplosis oryzae.

According to another way of working the processes according to theinvention, they are advantageously carried out for combating orcontrolling soil borne insect pests and notably those where at least oneliving stage is in the soil and during this stage cause damages tocrops.

Thus, among such soil borne insect pests can be mentioned Aeneolamiasp., Agrotis sp., Agriotes sp., Araecerus sp., Aulacophora sp.,Atherigona sp., Cerotoma sp., Chilo sp., Cylas sp., Delia sp.,Diabrotica sp., Diaprepes sp., Elasmopalpus sp., Frankliniella sp.,Graphognathus sp., Gryllotalpa sp., Hypomeces sp., Heteronychus sp.,Holotrichia sp., Hydraecia sp., Hylemia sp., Leucopholis sp., Lepidiotasp., Limonius sp., Listroderes sp., Loxostege sp., Mamestra sp.,Melolontha sp., Oscinella sp., Ostrinia sp., Otiorhynchus sp.,Phyllophaga sp., Phyllotreta sp., Popillia sp., Pseudococcus sp., Psilasp., Psylloides sp., Sitona sp., Spoladea sp., Tanymecus sp., Thrips andTribolium sp.

Or even, processes according to the invention are very advantageous:

against lepidopterans, notably Pectinophora gossypiella, Bupaluspiniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeutapadella, Plutella sp., e.g. Plutella xylostella, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria sp., e.g. Bucculatrix thurberiella,Phyllocnistis citrella, Agrotis sp., e.g. Agrotis segetum, Agrotisipsilon, Euxoa sp., Feltia sp., Earias insulana, Heliothis sp., e.g.Helicoverpa armigera, Helicoverpa armigera, Helicoverpa zea, Laphygmaexigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodopterasp., e.g. Spodoptera littoralis, Spodoptera litura, Spodoptera exigua,Trichoplusia ni, Cydia pomonella, Pieris sp., Chilo sp., e.g. Chilosuppressalis, Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana,Clysia ambiguella, Hofmannophila pseudospretella, Homona magnanima,Tineola bisselliella, Tinea pellionella, Elasmopalpus sp., Hydraeciasp., Loxostege sp., Ostrinia sp., Spoladea sp., e.g. Tortrix viridana;

against coleopterans, notably Anobium punctatum, Rhizopertha dominica,Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus,Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae,Diabrotica sp., e.g. Diabrotica undecimpunctata, Diabrotica virgifera,Psylloides chrysocephala, Epilachna varivestis, Atomaria sp., e.g.Atomaria linearis, Oryzaephilus surinamensis, Anthonomus sp., e.g.Anthonomus grandis, Otiorhynchus sulcatus, Cosmopolites sordidus,Ceuthorrynchus assimilis, Hypera postica, Dermestes sp., Trogoderma sp.,Anthrenus sp., Attagenus sp., Lyctus sp., e.g. Meligethes aeneus, Ptinussp., e.g. Niptus hololeucus, Gibbium psylloides, Tribolium sp., e.g.Tenebrio molitor, Agriotes sp., e.g. Agriotes lineatus, Conoderus sp.,e.g. Melolontha melolontha, Amphimallon solstitialis, Aeolus sp.,Araecerus sp., Aulacophora sp., Cerotoma sp., Chaetocnema sp., Cylassp., Diaprepes sp., Graphognathus sp., Heteronychus sp., Holotrichiasp., Hypomeces sp., Leucopholis sp., Lepidiota sp., Limonius sp.,Listroderes sp., Melanotus sp., Phyllotreta sp., Phyllophaga sp.,Popillia sp., Sitona sp., Tanymecus sp., e.g. Costelytra zealandica or

against dipterans and notably Drosophila melanogaster, Chrysomyxa sp.,Hypoderma sp., Tannia sp., Bibio hortulanus, Oscinella frit, Phorbiasp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula sp.,Tipula paludosa, Atherigona sp., Delia sp., Hylemia sp., Psila rosae,Tipula oleracea.

According to a preferred use of the processes according to theinvention, these processes are carried out to simultaneously combatseveral of the insect pests mentioned; in this case, the processes arereferred to as processes for controlling a group of damaging insects.

According to an even more preferred use, such processes for controllingor treating a group of damaging insects are carried out for thetreatment or protection of a given crop.

Even more preferably, the processes according to the invention arecarried out in processes for controlling or treating insects, whichravage rice crops.

The processes for controlling or combating the insect pests according tothe invention may be carried out at the various stages in the life ordevelopment of the insects, in particular to control the eggs, thelarvae, irrespective of their stage of development, the chrysalides orthe nymphs, or alternatively to control the arthropods or the insects atthe adult stage.

Moreover, the said processes may be carried out both against isolatedinsects and against colonies of the said insects, as well as duringinfestations with the said insects.

For their use in treatment or protection processes according to theinvention, the insecticidal compounds (A) and (B) are used in amountswhich may vary within a wide range, especially according to the type ofcrop and according to the virulence, nature and degree of the attack bythe insects, and also according to the climatic or soil conditions.

Advantageously, in the treatment or protection processes according tothe invention, the insecticidal compound (A), preferably Fipronil, isused in an amount ranging from 0.5 to 500 g/ha, preferably ranging from2 to 100 g/ha; as regards the insecticidal compound (B), which ispreferably one of the compounds chosen from bifenthrin, cyfluthrin,cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,theta-cypermethrin, zeta-cypermethrin, deltamethrin, fenpropathrin,fenvalerate, flumethrin, permethrin, phenothrin, tefluthrin,tralomethrin, flucythrinate and tau-fluvalinate, it is used in an amountranging from 0.5 to 1000 g/ha, preferably ranging from 1 to 500 g/ha.

Even more advantageously, in the treatment or protection processesaccording to the invention, the insecticidal compounds (A) and (B) areused simultaneously in respective amounts of between 2 and 100 g/ha forthe insecticidal compound (A) and between 1 and 500 g/ha for theinsecticidal compound (B).

The weight ratio A/B is generally between 0.0005 and 250, preferablybetween 0.05 and 10; the weight ratio B/A is, for its part, generallybetween 0.004 and 2000, preferably between 0.1 and 20.

As has just been pointed out, the ratio A/B is a weight ratio of theamounts of insecticidal compounds (A) and (B) used.

Where appropriate, and in a most preferred manner, in the processesaccording to the invention, the ratio between the amounts of fiproniland of deltamethrin used is between 0.1 and 5, preferably between 0.5and 3; similarly, the ratio between the amounts of fipronil and ofcypermethrin is between 0.05 and 10, preferably between 0.15 and 6.

As regards the amounts of insecticidal compounds (A) and (B) used in thetreatment or protection processes according to the invention by foliarapplication, particularly satisfactory results are obtained forapplications after dilution, in particular in water, of between 50 and1500 l/ha, preferably between 200 and 800 l/ha.

For their use in the treatment or protection processes according to thepresent invention, the insecticidal compounds (A) and (B) may be appliedsimultaneously, but may also be prepared extemporaneously at the time ofuse of the said processes according to the invention.

According to another embodiment of the said processes according to theinvention, the insecticidal compounds (A) and (B) can also be appliedseparately.

Another aspect of the present invention relates to insecticidalcompounds, which may be used in the processes according to the inventionwhich have been the subject of the above developments.

In a particularly advantageous manner, the compositions according to theinvention comprise an insecticidal compound (A) and an insecticidalcompound (B) as have been defined above.

Thus, the compositions according to the invention preferably comprise aninsecticidal compound (A) containing a pyrazole group, and aninsecticidal compound (B) from the pyrethroid family.

The compositions according to the present invention advantageouslycomprise an insecticidal compound (A) from the phenylpyrazole family.

More advantageously, the said compositions according to the inventioncomprise an insecticidal compound (A) of formula (I) in which:

R₁ represents —CN or the methyl radical or the radical —C(S)NH₂ or theradical —C(═N—Y)Z;

R₂ represents —S(O)_(n)R₃;

R₃ represents an alkyl or haloalkyl radical;

R₄ is selected from the group consisting of a hydrogen atom, a halogenatom and a radical which can be —NR₅R₆, —C(O)OR₇, —S(O)_(m)R₇, alkyl,haloalkyl, —OR₈ or —N═C(R₉)(R₁₀);

R₅ and R₆ are selected independently from a hydrogen atom, an alkyl orhaloalkyl radical, —C(O)alkyl, —C(O)OR₇ and —S(O)_(r)CF₃; or R₅ and R₆together form a divalent radical which can be interrupted by one or moreheterbatoms;

R₇ is selected from an alkyl radical and a haloalkyl radical;

R₈ is selected from an alkyl radical, a haloalkyl radical and a hydrogenatom;

R₉ is selected from a hydrogen atom and an alkyl radical;

R₁₀ is selected from a phenyl radical and heteroaryl radical optionallysubstituted with one or more hydroxyl radicals, halogen atoms,—O-alkyls, —S-alkyls, cyano or alkyl radicals or a combination thereof;

X is selected from the nitrogen atom and the radical C—R₁₂;

Y is selected from the hydroxyl, amino, aminocarbonyl, alkoxy,arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl,alkylcarbamoyl and pyrazole groups, substituted or unsubstituted;

Z is selected from the hydroxyl, amino, aminocarbonyl, alkoxy,arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyland alkylcarbamoyl groups;

R₁₁ and R₁₂ are selected independently from a halogen atom and ahydrogen atom;

R₁₃ is selected from a halogen atom, a haloalkyl or haloalkoxy radical,—S(O)_(q)CF₃ and —SF₅;

m, n, q and r are selected independently from 0, 1 and 2;

with the proviso that, if R₁ represents the methyl radical, then R₃represents a haloalkyl radical, R₄ represents —NH₂, R₁₁ represents Cl,R₁₃ represents —CF₃ and X represents N;

the alkyl and alkoxy radicals of the formula (I) are preferably loweralkyl and alkoxy radicals, i.e. radicals possessing from one to fourcarbon atoms;

the haloalkyl and haloalkoxy radicals likewise possess preferably fromone to four carbon atoms;

the haloalkyl and haloalkoxy radicals can carry one or more halogenatoms; the preferred radicals of this type comprise —CF₃ and —OCF₃.

According to another preferred embodiment, the compositions according tothe invention comprise an insecticidal compound (A) of formula (I) inwhich:

R₁ represents —CN; and/or

R₄ represents —NR₅R₆; and/or

R₅ and R₆ are selected independently from a hydrogen atom, an alkyl orhaloalkyl radical, —C(O)alkyl and C(O)OR₇; and/or

X represents —C—R₁₂; and/or

R₁₃ is selected from a halogen atom, a haloalkyl or haloalkoxy radicaland —SF₅.

In accordance with another especially advantageous embodiment, thecompositions according to the invention comprise Fipronil, chemical name5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole,as insecticidal compound (A).

As regards the compounds of the pyrethroid family which are usually usedas insecticidal compound (B) in the compositions according to theinvention, the ones preferably used are those of formula (II) in which:

R₁ and R₂ represent, independently, a C₁ to C₈ alkyl radical or a C₁ toC₈ haloalkyl radical or a halogen atom or a substituted or unsubstitutedphenyl group;

R₃ represents a —CN group or a hydrogen atom or a C₁ to C₈ alkylradical;

R₄ represents a substituted or unsubstituted phenyl group.

Advantageously and according to another embodiment of the compositionsaccording to the invention, the compound (B) used is a compound offormula (II) in which:

R₁ and R₂ represent, independently, a bromine atom or a chlorine atom ora methyl radical or an isopropyl radical or a para-chlorophenyl radicalor a trifluoromethyl radical; and/or

R₄ represents a substituted or unsubstituted phenoxybenzyl group.

Another advantageous embodiment of the compositions according to theinvention uses a compound (B) of formula (II) in which:

R₄ represents a halophenoxybenzyl group.

Where appropriate, and in the compositions according to the invention,the compound (B) of formula (II) can be used either in the form of aspecific isomer or in the form of a mixture of several isomers, or evenin the form of a mixture of several compounds of formula (II).

However, as regards the compounds of the pyrethroid family which areused as insecticidal compound (B) in the compositions according to theinvention, the ones preferably used are the compounds chosen from thegroup comprising:

bifenthrin or2-methylbiphenyl-3-ylmethyl-(Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate,especially in an A/B ratio of between 0.25 and 0.9;

cyfluthrin or (R,S)-α-cyano-4-fluoro-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,especially in an A/B ratio of between 0.25 and 0.9;

cyhalothrin or (R,S)-α-cyano-3-phenoxybenzyl(Z)-(1RS,3RS)-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate,especially in an A/B ratio of between 0.1 and 5;

cypermethrin or (R,S)-α-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,especially in an A/B ratio of between 0.25 and 0.9;

alpha-cypermethrin or racemic mixture comprising(S)-α-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(R)-α-cyano-3-phenoxybenzyl(1S,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

beta-cypermethrin or reaction mixture comprising, in a 2:3 ratio, the 2enantiomeric pairs (S)-α-cyano-3-phenoxybenzyl(1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(R)-α-cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate with(S)-α-cyano-3-phenoxybenzyl(1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(R)-α-cyano-3-phenoxybenzyl(1S)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;

theta-cypermethrin or mixture of the enantiomers(R)-α-cyano-3-phenoxybenzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and(S)-α-cyano-3-phenoxybenzyl(1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate in a1:1 ratio;

zeta-cypermethrin or mixture of the stereoisomers(S)-α-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,in which mixture the ratio of the enantiomeric pairs (S)-(1RS,3RS) and(S)-(1RS,3SR) is, respectively, between 45/55 and 55/45;

deltamethrin or (S)-α-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate;

fenpropathrin or (RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate, especially in a ratio ofbetween 0.1 and 5;

fenvalerate or (RS)-α-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methylbutyrate, especially in a ratio ofbetween 0.15 and 0.45;

flumethrin or α-cyano-4-fluoro-3-phenoxybenzyl;

permethrin or 3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,especially in a ratio of between 0.1 and 0.8;

phenothrin or 3-phenoxybenzyl(1RS,3RS;1RS,3SR)-2,2-dimethyl-3-(2-methylprop-1-enyl)-cyclopropanecarboxylate;

tefluthrin or 2,3,5,6-tetrafluoro-4-methylbenzyl(Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate,especially in a ratio of between 0.1 and 5;

tralomethrin or (S)-α-cyano-3-phenoxybenzyl(1R,3S)-2,2-dimethyl-3-[(RS)-1,2,2,2-tetrabromoethyl]-cyclopropanecarboxylate,especially in a ratio of between 0.6 to 0.9;

flucythrinate or (RS)-α-cyano-3-phenoxybenzyl(S)-2-(4-difluoromethoxyphenyl)-3-methylbutyrate;

tau-fluvalinate or (RS)-α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate.

Usually, the insecticidal compounds (A) and (B) used in the compositionsaccording to the invention are combined with one or more supports and/orwith one or more substances that are useful for formulating them. Thus,where appropriate, the compositions according to the invention cancomprise up to 99% of support and/or up to 25% of one or moresurfactants and/or up to 25% of one or more formulation agents.

Usually also, the compositions according to the invention comprisebetween 0.00001% and 100%, preferably between 0.001% and 80%, ofinsecticidal compounds (A) and (B), whether these compounds arecombined, or whether they are in the form of two active materials usedseparately.

When they use two active materials (A) and (B) together, the saidcompositions according to the invention can do so in amounts asdescribed above, but also for ratios A/B of between 0.0005 and 250,preferably between 0.05 and 10.

For their use in the compositions according to the invention, thecompounds (A) and (B) are usually combined with one or more supports,optionally with one or more surfactants and optionally with one or moreformulation agents or auxiliaries.

In the present description, the term “support” denotes an organic ormineral, natural or synthetic material with which the active material(s)(A) and/or (B) are [lacuna] in the compositions according to theinvention, especially to facilitate their application to a plant, oralternatively to seeds or to the soil.

This support is thus generally inert and it should, usually, beagriculturally acceptable, in particular to the treated plant.

The support which may be used for the formulation of the compounds (A)and/or (B) in the processes according to the invention may be solid orliquid.

As examples of solid supports which may be used, mention may be made ofnatural or synthetic silicates, resins, waxes, fine powders or granulesof clay, in particular of kaolin clay, of diatomaceous earth, ofbentonite or of acidic clay, synthetic hydrated silicon oxide, talcs,ceramics, other minerals including sericite, quartz, sulphur, activecharcoal, calcium carbonate and hydrated silica, or industrialfertilizers such as ammonium sulphate, ammonium phosphate, ammoniumnitrate, urea or ammonium chloride.

As examples of liquid supports which may be used, mention may be made ofwater, alcohols and especially methanol or ethanol, ketones andespecially acetone, methyl ethyl ketone or cyclohexanone, petroleumfractions, aromatic hydrocarbons including benzene, toluene, xylene,ethylbenzene or methylnaphthalene, non-aromatic hydrocarbons includinghexane, cyclohexane, kerosene or gas oil, liquefied gas, estersincluding ethyl acetate and butyl acetate, nitrites includingacetonitrile and isobutyronitrile, ethers including diisopropyl etherand dioxane, amides including N,N-dimethylformamide andN,N-dimethylacetamide, halogenated hydrocarbons includingdichloromethane, trichloroethane and carbon tetrachloride, dimethylsulphoxide, and plant oils including soybean oil and cotton oil.

The surfactant(s) may be emulsifiers, dispersants or wetting agents ofionic or nonionic type.

Mention may be made, for example, of polyacrylic acid salts,lignosulphonic acid salts, phenolsulphonic acid salts ornaphthalenesulphonic acid salts, polycondensates of ethylene oxide withfatty alcohols or fatty acids or fatty amines, substituted phenols, inparticular alkylphenols or arylphenols, salts of sulphosuccinic acidesters, taurine derivatives, in particular alkyltaurates,polyoxyethylated phosphoric esters of alcohols or of phenols; mentionmay be made most particularly of the salts of alkylsulphonates,alkylarylsulphonates, alkylaryl ethers, polyoxyethylenic derivativesthereof, polyethylene glycol ethers, polyalcohol esters, sugarderivatives, alcohols and the like.

The presence of at least one surfactant is generally essential when atleast one of the active materials and/or the inert support is insoluble,especially in water when the vector agent for the application is water.

In the compositions according to the invention all kinds of otheringredients or agents may also be combined with the compounds (A) and/or(B) such as, for example, protective colloids, adhesives, thickeners,thixotropic agents, penetrating agents, stabilizers including isopropylhydrogen phosphate, 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol, mineralor plant oils, fatty acids or esters thereof, sequestering agents,dispersants including casein, gelatin, saccharides and in particularstarch powder, gum arabic, certain cellulose derivatives or alginicacid, lignin derivatives, bentonite, water-soluble synthetic polymers,in particular polyvinyl alcohol, polyvinylpyrrolidone, polyacrylicacids, etc., and also other active materials known for their pesticidalproperties, in particular insecticides or fungicides; or for theirproperties of promoting plant growth, especially fertilizers; or fortheir regulatory properties on plant or insect growth.

The insecticidal compositions according to the invention may take quitea wide variety of forms, and may especially be in solid or liquid forms.

Thus, the said compositions according to the invention can take the formof relatively numerous formulations, among which mention may be made ofoily solutions, emulsifiable concentrates, wettable powders, fluidformulations and especially aqueous suspensions or aqueous emulsions,granules, powders, aerosols, fumigenic formulations includingself-combustible fumigenic formulations or fumigenic formulationsinvolving a chemical reaction, formulations for nebulization, inparticular formulations for misting, formulations with a very lowvolume, pastes, emulsions, concentrated suspensions, and also possiblemixtures, associations or combinations of these various forms.

Usually, for the formulations such as the powders for dusting ordispersion, the content of insecticidal compounds (A) and (B) can be upto 100%; similarly, for the formulations in the form of granules,especially those obtained by extrusion, compacting, impregnation of agranular support or granulation using a powder, the content ofinsecticidal compounds (A) and (B) in these granules according to theinvention is usually between 0.5% and 80%.

The insecticidal compositions according to the invention, referred to asconcentrated compositions, comprising an insecticidal compound (A) andan insecticidal compound (B) which are in the form of emulsifiableconcentrates or soluble concentrates, usually comprise from 25% to 100%of active materials; the ready-to-apply emulsions or solutionsthemselves contain from 0.00001% to 20% of active materials.

It goes without saying that the expression “active materials” should beunderstood throughout the present description as, where appropriate, anactive material or insecticidal compound (A) or (B) alone, but also as acombination of these two active materials.

In addition to the solvent, the emulsifiable concentrates may contain,when necessary, 2% to 20% of suitable additives such as the stabilizers,surfactants, penetrating agents, corrosion inhibitors, colorants oradhesives mentioned above.

The insecticidal compositions according to the invention in the form ofconcentrated suspensions, which can also be applied by spraying, areprepared so as to obtain a stable fluid product which does not sedimentout; they usually contain from 2% to 75% of active materials, from 0.5%to 15% of surfactants, from 0.1% to 10% of thixotropic agents, from 0%to 10% of suitable additives, such as antifoams, corrosion inhibitors,stabilizers, penetrating agents and adhesives, and, as support, water oran organic liquid in which the active material(s) is(are) insoluble oronly sparingly soluble, or alternatively mixtures of several of theseorganic or inorganic solvents.

Certain solid organic materials or mineral salts may be dissolved in thesupport to halt or prevent the sedimentation; or alternatively suchmaterials may be used as antifreezes for the water.

The insecticidal compositions according to the invention which take theform of wettable powders or powders for spraying are usually preparedsuch that they contain from 20% to 95% of active materials.

Moreover, they usually contain, besides a solid support, from 0% to 5%of a wetting agent, from 3% to 10% of a dispersant, and, whereappropriate, from 0% to 10% of one or more stabilizers and/or otheradditives, such as penetrating agents, adhesives, anticaking agents,colorants, etc.

To obtain these powders for spraying or wettable powders, the activematerial(s) is(are) intimately mixed in suitable mixers with theadditional substances, and are ground using mills or other suitablegrinders. Powders for spraying are thus obtained with particularlyadvantageous wettability and suspendability; they can be suspended inwater to any desired concentration.

Rather than wettable powders, it is possible to prepare insecticidalcompositions according to the invention which are in the form of pastes.

The conditions and modes of preparation and of use of these pastes aresimilar to those for the wettable powders or powders for spraying.

As has just been stated, the aqueous dispersions and emulsions, forexample the insecticidal compositions obtained by diluting a wettablepowder or an emulsifiable concentrate according to the invention withwater, are included in the general scope of the present invention.

The emulsions may be of the water-in-oil or oil-in-water type and theymay have a thick or relatively thick consistency.

More generally, the compositions according to the invention may be innumerous formulation forms; thus, it is possible to use thesecompositions comprising an insecticidal compound (A) and an insecticidalcompound (B) as an aerosol generator; lure (ready-to-use); concentratefor preparing lures; stock lure; capsule suspension; cold-nebulizationproduct; powder for dusting; emulsifiable concentrate; emulsion ofaqueous/aqueous type; emulsion of oily/reverse type; encapsulatedgranule; fine granule; concentrated suspension for seed treatment;compressed gas; gas-generating product; lure on grain; granulated lure;granule; hot-nebulization product; macrogranule; microgranule; powder tobe dispersed in oil; concentrated suspension dilutable in oil;oil-miscible liquid; paste; stick for agropharmaceutical use; lure onbricks; powder for dry-treating seeds; lure on chunks; treated or coatedseeds; fumigenic candle; fumigenic cartridge; fumigen; fumigenicgranule; fumigenic stick; fumigenic tablet, fumigenic dish; solubleconcentrate; soluble powder; liquid for treating seeds; concentratedsuspension (=fluidizable concentrate); lain powder; very-low-volumeliquid for application; very-low-volume suspension for application;vapour-diffuser product; granules or tablets to be dispersed in water;wettable powder for wet treatment; water-soluble granules or tablets;soluble powder for seed treatment; wettable powder.

According to another embodiment of the present invention, the variousinsecticidal compositions according to the invention which it has beenpossible to describe above may also take the form of extemporaneousmixtures, commonly referred to as tank mixes.

These insecticidal compositions in the form of tank mixes are usually inthe form of dilute insecticidal compositions.

In this case, the insecticidal compositions according to the inventionare in the form of insecticidal compositions separately comprising theinsecticidal compounds (A) and (B), the said insecticidal compositionsthus needing to be mixed together when they are applied or when thedilute insecticidal composition to be applied is prepared.

These insecticidal compositions known as tank mixes are usually mixed inthe tank of the application device.

However, these said insecticidal compositions separately comprising theinsecticidal compounds (A) and (B) may also be applied separately, inparticular after dilution, thus making it possible to obtain theproperties of the insecticidal compositions according to the inventioncomprising the said insecticidal compounds (A) and (B) directly on thesites of application.

It goes without saying that the different variants or embodiments whichmay be envisaged both for the compositions and for the treatment and/orprotection processes according to the invention form an integral part ofthe present invention; the said different variants may moreover becombined or associated with each other without, however, departing fromthe spirit or scope of the said invention.

In the same manner, the various aspects of the present invention whichhave just been described may be combined or associated with each otherwithout, however, departing from the spirit or scope of the saidinvention.

The examples which follow will allow a better illustration of thevarious aspects of the present invention, in particular of the aspectsrelating to the processes and to the compositions according to theinvention using the said insecticidal compositions. However, theseexamples do not in any way limit the scope of the present invention.

The process examples A to L which follow will give an illustration ofspecific processes according to the invention.

These process examples will also make it possible to highlight manyadvantages intrinsic to the processes according to the invention.

PROCESS EXAMPLE A

This process example proposes to give an illustration of an insecticidaltreatment process according to the invention.

The treatment process carried out was a treatment process against yellowrice stem borer or Tryporyza incertulas during the infestation of a ricecrop. For the comparison of the process according to the invention withknown insecticidal treatment processes, four plots were prepared in asimilar manner.

The first is left without treatment, the second is treated with fipronilas active material, the third with deltamethrin and the fourth withfipronil and deltamethrin in accordance with the process according tothe invention.

After sowing and then growing, the rice seedlings are transplanted atthe three- to four-leaf stage.

The various active materials were then applied 7 days after plantingout.

The formulation used in this process according to the invention isidentical to that of Composition Example A.

The application rates and the results obtained are collated in Table 1.

The measurement was carried out by counting the number of rice plantcores that were dead due to attack by the damaging insects treated, i.e.Tryporyza incertulas; thus, the smallest number is obtained aftercarrying out the process according to the invention, while the untreatedplots or plots treated in a known manner give substantially largernumbers.

These results thus show that the process according to the invention hasbetter insecticidal efficacy while at the same time allowing asubstantial reduction in the amounts of active materials spread and,concomitantly, a reduction in the environmental impact.

TABLE 1 Plot Plot Plot Plot No. 1 No. 2 No. 3 No. 4 Active material Nofipronil deltamethrin fipronil and used in the treatment deltamethrinprocess carried out Rate of / 10 g/ha 6 g/ha 11 g/ha application of ofwhich active material 5 g/ha of in the process fipronil and 6 g/ha ofdeltamethrin Proportion of dead 78% 56% 66% 54% plant cores found

This process example thus gives a perfect illustration of the advantagesarising from the use of the process according to the invention, inparticular on account of the very satisfactory insecticidal efficacyagainst the damaging insect treated, but also on account of thereduction in the amounts of active materials spread.

PROCESS EXAMPLE B

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against leafhoppersand in particular against Nephotettix apicalis.

This process according to the invention was carried out for thetreatment of a rice crop.

The operating conditions were reproduced and adapted from those ofProcess Example A.

The active materials used were fipronil and deltamethrin in aformulation in the form of granules according to Composition Example A.

The active material(s) was(were) applied to the plots 25 days afterplanting out.

The rates of active materials applied and the results obtained 14 daysafter application are collated in Table 2.

TABLE 2 Plot Plot Plot No. 1 No. 2 No. 3 Active material fipronildeltamethrin fipronil and used in the deltamethrin process carried outRate of 25 g/ha 6 g/ha 11 g/ha application of of which 5 g/ha activematerial of fipronil and in the process 6 g/ha of deltamethrinInsecticidal efficacy 16% 6% 28%

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amount of activematerial spread.

PROCESS EXAMPLE C

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against Nilaparvatalugens. The operating and measuring conditions are reproduced andadapted from Process Example B.

The application rates and the results are collated in Table 3.

TABLE 3 Plot Plot Plot No. 1 No. 2 No. 3 Active material fipronilcypermethrin fipronil and used in the cypermethrin Process carried outRate of 10 g/ha 12.5 g/ha 17.5 g/ha application of of which 5 g/haactive material of fipronil and in the process 12.5 g/ha of cypermethrinInsecticidal 78% 21% 76% efficacy

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amounts of activematerials spread.

PROCESS EXAMPLE D

This process example according to the invention gives an illustration ofthe improvement in the yield of a rice crop obtained concomitantly withthe control of the insects which ravage this rice crop.

In this treatment Process Example according to the invention, the yieldof the crop was evaluated, along with the improvement in this yieldobtained by carrying out the said process according to the inventionsimultaneously using fipronil as compound (A) and cypermethrin ascompound (B).

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The application rates and the results are collated in Table 4.

TABLE 4 Plot Plot Plot Plot No. 1 No. 2 No. 3 No. 4 Active materialfipronil cypermethrin fipronil and No used in the cypermethrin treatmentprocess carried out Rate of 10 g/ha 12.5 g/ha 17.5 g/ha / application ofof which active material 5 g/ha in the process of fipronil and 12.5 g/haof cypermethrin Yield of the 2.276 1.416 2.596 791 plot (kg/ha)Improvement in 188 78 228 / the yield of the plot (%)

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms of absoluteyield and in terms of relative yield on account of the improvementobtained during the use of the process according to the invention, andalso in terms of reduction in the amounts of active materials spread.

PROCESS EXAMPLE E

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against Nilaparvatalugens.

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 5.

TABLE 5 Plot Plot Plot No. 1 No. 2 No. 3 Active material used fipronildeltamethrin fipronil and in the process carried deltamethrin out Rateof application of 25 g/ha 6 g/ha 8 g/ha active material of which in theprocess 5 g/ha of fipronil and 3 g/ha of deltamethrin Degree ofvariation in +33% +27% −40% the number of damaging insects 3 days afterapplication Degree of variation in +11%    0% −20% the number ofdamaging insects 7 days after application

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amounts of activematerials spread.

Specifically, only the treatment process according to the inventionusing fipronil and deltamethrin as compounds (A) and (B) makes itpossible to achieve a reduction in the number of damaging insects.

PROCESS EXAMPLE F

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against Nilaparvatalugens.

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 6.

TABLE 6 Plot Plot Plot No. 1 No. 2 No. 3 Active material used fipronilcypermethrin fipronil and in the process cypermethrin carried out Rateof application 25 g/ha 12.5 g/ha 17.5 g/ha of active material of whichin the process 5 g/ha of fipronil and 12.5 g/ha of cypermethrin Degreeof variation +33% −27% −41% in the number of damaging insects 3 daysafter application Degree of variation +11% +13% −47% in the number ofdamaging insects 7 days after application

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amounts of activematerials spread.

Specifically, only the treatment process according to the inventionusing fipronil and cypermethrin as compounds (A) and (B) makes itpossible to achieve a reduction in the number of damaging insects.

PROCESS EXAMPLE G

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against Nephotettixapicalis. The operating and measuring conditions are reproduced andadapted from Process Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 7.

TABLE 7 Plot Plot Plot Plot No. 1 No. 2 No. 3 No. 4 Active materialfipronil deltamethrin fipronil and No used in the deltamethrin treatmentprocess carried out Rate of 25 g/ha 6 g/ha 8 g/ha / application of ofwhich active material 5 g/ha in the process of fipronil and 3 g/ha ofdeltamethrin Degree of  +50% −13% −53% +200% variation in the number ofdamaging insects 1 day after application Degree of  +83% +25% −32% +200%variation in the number of damaging insects 3 days after applicationDegree of +183% +75% +11% +522% variation in the number of damaginginsects 7 days after application

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amounts of activematerials spread.

PROCESS EXAMPLE H

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against Nilaparvatalugens.

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 8.

TABLE 8 Plot Plot Plot No. 1 No. 2 No. 3 Active material used fipronilfipronil and No in the process cypermethrin treatment carried out Rateof application 25 g/ha 25 g/ha / of active material of which in theprocess 5 g/ha of fipronil and 20 g/ha of cypermethrin Degree ofvariation −15% −49%  +65% in the number of damaging insects 1 day afterapplication Degree of variation  −8% −23%  +34% in the number ofdamaging insects 3 days after application Degree of variation −16% −28% +42% in the number of damaging insects 7 days after application Degreeof variation +40% +26% +108% in the number of damaging insects 14 daysafter application

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amounts of activematerials spread.

PROCESS EXAMPLE I

This process example gives an illustration of a process according to theinvention which is useful for insecticidal treatment against Nilaparvatalugens.

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 9.

TABLE 9 Plot Plot Plot No. 1 No. 2 No. 3 Active material used fipronilfipronil and No in the process cypermethrin treatment carried out Rateof application 25 g/ha 25 g/ha / of active material of which in theprocess  5 g/ha of fipronil and 20 g/ha of cypermethrin Degree ofvariation +19% −14% +113% in the number of damaging insects 7 days afterapplication

The results obtained during the use of this process according to theinvention are thus particularly satisfactory, both in terms ofinsecticidal efficacy and in terms of reduction in the amounts of activematerials spread.

PROCESS EXAMPLE J

This process example proposes to give an illustration of an insecticidaltreatment process according to the invention.

The treatment process used was a process of treatment against yellowrice stem borer or Tryporyza incertulas during the infestation of a ricecrop.

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 10.

TABLE 10 Plot Plot Plot No. 1 No. 2 No. 3 Active material used Nofipronil fipronil and in the process treatment cypermethrin carried outRate of application / 25 g/ha 25 g/ha of active material of which in theprocess  5 g/ha of fipronil and 20 g/ha of cypermethrin Degree ofvariation −26% −35% −66% in the number of dead plant cores

The measurement was carried out by counting the number of rice plantcores that were dead due to attack by the damaging insects treated, i.e.Tryporyza incertulas; thus, the greatest degree of reduction is obtainedafter carrying out the process according to the invention, whereas theuntreated plots or plots treated in a known manner give substantiallymore mediocre degrees.

These results thus show that the process according to the invention isof superior insecticidal efficacy while at the same time allowing asubstantial reduction in the amounts of active materials spread and,concomitantly, a reduction in the environmental impact.

PROCESS EXAMPLE K

This process example proposes to give an illustration of an insecticidaltreatment process according to the invention.

The treatment process used was a process of treatment againstScotinophara lurida during the infestation of a rice crop.

The operating and measuring conditions are reproduced and adapted fromProcess Example B.

The active materials used, their application rates and the resultsobtained are collated in Table 11.

TABLE 11 Plot Plot Plot No. 1 No. 2 No. 3 Active material used Nofipronil fipronil and in the process treatment cypermethrin carried outRate of application / 25 g/ha 25 g/ha of active material of which in theprocess  5 g/ha of fipronil and 20 g/ha of cypermethrin Degree ofvariation −21% −43% −52% in the number of damaging insects 1 day aftertreatment Degree of variation −40% −67% −81% in the number of damaginginsects 3 days after treatment Degree of variation −27% −45% −60% in thenumber of damaging insects 14 days after treatment

These results thus show that the process according to the invention isof higher insecticidal efficacy while at the same time allowing asubstantial reduction in the amounts of active materials spread and,concomitantly, a reduction in the environmental impact.

PROCESS EXAMPLE L

Maize seeds (variety Lorenzo) in a container under agitation weretreated with the active ingredients, alone and in combination. Threetreated seeds were sown in a 10-cm diameter pot. A week after sowing,each pot was infected with 10 L2 larvae of Agrotis segetum (turnipmoth). The efficacy of the active ingredients at preventing feedingdamage was determined 42 days after sowing. The test was carried out ina glasshouse at 22-27° C. and 30-70% relative humidity.

To indicate the existence of synergism between the active components theresults were treated in the manner described by Colby S. R.,“Calculating Synergistic and Antagonistic Responses of HerbicideCombinations” in Weeds 1967 15, 20-22. In this method the “expected”percent control of damage, E, of the combination compared with untreatedcontrol is given by the equation

E=D+F−DF/100

where D is the % control by deltamethrin used alone at a givenconcentration and F is the % control by fipronil, used alone at a givenconcentration. If the observed control of the mixture is greater than Ethe results indicate synergism. The results are shown in the followingtable.

TABLE 12 Table (Average of 3 treatments) Active Expected ingredient RateControl (E) (formulation) (g a.i./kg seed) (% efficacy) (%) Untreated —0 fipronil (FS 2, 5 50 500 g/l) deltamethrin 0, 5 40 (SC 50 g/l)fipronil (FS 2, 5 + 0, 5 90 70 500 g/l) + deltamethrin (SC 50 g/l)

In a particularly satisfactory manner, the results obtained in thevarious processes according to the invention carried out in ProcessExamples A to L required only a single application of the activematerials (A) and (B) used, whereas, in the known usual practise, it iscommon to make use of several applications in order to achieve anacceptable or equivalent result.

Composition Examples A to G illustrate specific insecticidalcompositions according to the invention.

COMPOSITION EXAMPLE A

According to a composition example according to the invention in theform of granules, the following constituents are used:

22.7 g of fipronil as insecticidal compound (A)   50 g and 27.3 g ofdeltamethrin as insecticidal compound (B) epichlorohydrin  2.5 g cetylpolyglycol ether  2.5 g polyethylene glycol   35 g kaolin with aparticle size of between 0.3 and  910 g 0.8 mm

In this particular case, the insecticidal active materials are mixedwith the epichlorohydrin and 60 g of acetone are added, followed byaddition of the polyethylene glycol and the cetyl polyglycol ether. Thekaolin is sprinkled with the solution obtained and the acetone is thenevaporated off under vacuum.

COMPOSITION EXAMPLE B

According to a composition example according to the invention in theform of granules, the following constituents are used:

14.3 g of fipronil as insecticidal compound (A)   50 g and 35.7 g ofcypermethrin as insecticidal compound (B) epichlorohydrin  2.5 g cetylpolyglycol ether  2.5 g polyethylene glycol   35 g kaolin with aparticle size of between 0.3 and  910 g 0.8 mm

The process is then performed as described for Composition Example A.

COMPOSITION EXAMPLE C

This example proposes to illustrate a composition according to theinvention, which is in the form of an emulsifiable concentrate.

7.2 g of fipronil as insecticidal compound (A) 25 g and 17.8 g ofcypermethrin as insecticidal compound (B) tristyrylphenol/ethylene oxidecondensate 10 g solution containing 70% by weight/volume of  5 g calciumdodecylbenzenesulphonate N-methylpyrrolidone 50 g light C₁₀ aromaticsolvent 10 g

The first three components are dissolved in the N-methylpyrrolidone; thelight C₁₀ aromatic solvent is then added to adjust to the final volume.

COMPOSITION EXAMPLE D

Another specific insecticidal composition according to the invention,which is in the form of an emulsifiable concentrate, is prepared usingthe following components:

15.6 g of fipronil as insecticidal compound (A) 25 g and 9.4 g ofdeltamethrin as insecticidal compound (B) tristyrylphenol/ethylene oxidecondensate 10 g solution containing 70% by weight/volume of  5 g calciumdodecylbenzenesulphonate N-methylpyrrolidone 50 g light C₁₀ aromaticsolvent 10 g

The process is then performed as described for Composition Example C.

COMPOSITION EXAMPLE E

According to a composition example according to the invention in theform of granules, the following constituents are used:

10 g of fipronil as insecticidal compound (A)   50 g and 40 g ofcypermethrin as insecticidal compound (B) epichlorohydrin  2.5 g cetylpolyglycol ether  2.5 g polyethylene glycol   35 g kaolin with aparticle size of between 0.3 and  910 g 0.8 mm

The process is then performed as described for Composition Example A.

COMPOSITION EXAMPLE F

According to another specific composition example according to theinvention in the form of water-dispersible granules, the followingconstituents are used:

81.9 g of fipronil as insecticidal compound (A)  180 g and 98.1 g ofdeltamethrin as insecticidal compound (B) sodium lignosulphonate   27 galkylnaphthalenesulphonates condensate   18 galkylnaphthalenesulphonates  4.5 g

The ingredients are mixed together, micronized in a fluid-energy milland then granulated in a rotary granulator by spraying with water (up to10%). The granules thus obtained are dried in a fluidized-bed dryer inorder to remove the excess water.

COMPOSITION EXAMPLE G

According to another specific composition example according to theinvention in the form of water-dispersible granules, the followingconstituents are used:

36 g of fipronil as insecticidal compound (A)  180 g and 144 g ofcypermethrin as insecticidal compound (B) sodium lignosulphonate   27 galkylnaphthalenesulphonates condensate   18 galkylnaphthalenesulphonates  4.5 g

The process is then performed as described for Composition Example F.

The Compositions Examples A to G, and also the Process Examples A to L,which have just been given clearly illustrate the superiority of thecompositions and processes according to the invention over the knowninsecticides (A) and (B) alone.

The combination of the said process examples also allows a perfectillustration of the advantages provided by the treatment processesaccording to the invention, by means of compositions according to theinvention comprising an insecticidal compound (A) and an insecticidalcompound (B).

Satisfactory results are also obtained when insecticidal compositionsaccording to the invention in the form of one or other of theinsecticidal compositions according to the invention, in particularthose illustrated by Composition Examples A to G, are used for thetreatment processes according to the invention.

Moreover, no phytotoxicity phenomenon is observed in these processexamples during treatments using the various insecticidal compositionsaccording to the invention.

What is claimed is:
 1. A process for killing rice-damaging arthropods inrice plants, comprising applying to said rice plants or to the soil inwhich they grow, a synergistically arthropodicidally effective amount ofa combination of the insecticidal compound fipronil, which is5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole,as compound (A), and an insecticidal compound (B) which is deltamethrinor cypermethrin, wherein the A/B weight ratio is between 0.1 and 5 whencompound (B) is deltamethrin and between 0.05 and 10 when compound (B)is cypermethrin, and wherein from 0.5 to 500 g/ha of compound (A) andfrom 0.5 to 1000 g/ha of compound (B) are applied.
 2. A processaccording to claim 1, wherein from 2 to 100 g/ha of compound (A) andfrom 1 to 500 g/ha of compound (B) are applied.
 3. A process accordingto claim 1, wherein the A/B weight ratio is between 0.5 and 3 whencompound (B) is deltamethrin, and between 0.15 and 6 when compound (B)is cypermethrin.
 4. A process according to claim 2, wherein the A/Bweight ratio is between 0.5 and 3 when compound (B) is deltamethrin, andbetween 0.15 and 6 when compound (B) is cypermethrin.
 5. A processaccording to claim 1, wherein the arthropods are selected from the groupconsisting of Tryporyza incertulas, Nephotettix apicalis, Nilaparvatalugens and Scotinophara lurida.
 6. A process according to claim 2,wherein the arthropods are selected from the group consisting ofTryporyza incertulas, Nephotettix apicalis, Nilaparvata lugens andScotinophara lurida.
 7. A process according to claim 3, wherein thearthropods are selected from the group consisting of Tryporyzaincertulas, Nephotettix apicalis, Nilaparvata lugens and Scotinopharalurida.
 8. A process according to claim 4, wherein the arthropods areselected from the group consisting of Tryporyza incertulas, Nephotettixapicalis, Nilaparvata lugens and Scotinophara lurida.
 9. A processaccording to claim 3, wherein compound (B) is cypermethrin and whereinthe A/B weight ratio is between 0.25 and 0.9.
 10. A process according toclaim 4, wherein compound (B) is cypermethrin and the A/B weight ratiois between 0.25 and 0.9.
 11. A process according to claim 5, whereincompound (B) is cypermethrin and wherein the A/B weight ratio is between0.25 and 0.9.